Aluminum chelate compound and room temperature-curable resin composition containing same

ABSTRACT

Provided are an aluminum chelate compound useful as, for example, a curing catalyst for a room temperature-curable resin; and a room temperature-curable resin composition containing such aluminum chelate compound. 
     This aluminum chelate compound is an aluminum chelate compound having a β-dicarbonyl compound represented by the following general formula (1): 
     
       
         
         
             
             
         
       
     
     (wherein each of R 1  to R 3  represents a monovalent hydrocarbon group or a halogen atom; R 4  represents a hydrogen atom or a monovalent hydrocarbon group; and A is a group selected from a group represented by the following formula (2) and a group represented by —OR 8 : 
     
       
         
         
             
             
         
       
     
     wherein each of R 5  to R 7  represents a monovalent hydrocarbon group or a halogen atom; and R 8  represents a monovalent hydrocarbon group).

TECHNICAL FIELD

The present invention relates to an aluminum chelate compound useful as,for example, a catalyst of a room temperature-curable resin; and a roomtemperature-curable resin composition containing the same. Particularly,the present invention relates to a room temperature-curableorganopolysiloxane composition as well as a molded product obtained bycuring such composition.

BACKGROUND ART

A β-diketo compound enabling keto-enol transformation is capable offorming a complex compound with aluminum in an enol structure. That is,there is produced an aluminum chelate compound as a compound containinga β-diketo group(s). Because an alkyl group(s) bonded to a β-diketogroup(s) is usually included in a β-diketo compound, such aluminumchelate compound also has an affinity for many kinds of organicpolymeric materials. For this reason, such aluminum chelate compound hasbeen used in compositions containing organic polymeric materials, suchas paints, adhesive agents and inks, and has endowed these compositionswith various types of properties. For example, such aluminum chelatecompound is used as a catalytic composition for a roomtemperature-curable resin.

As such a kind of aluminum chelate compound, there has been known, forexample, a monoacetylacetonate aluminum bis (ethylacetoacetate) 76%isopropanol solution. Patent document 1 discloses, for example, a methodfor synthesizing such aluminum chelate compound. However, such knownaluminum chelate compound often exhibits a low activity when used as acuring catalyst for a sealant or the like. That is, such known aluminumchelate compound may not necessarily be the most appropriate optiondepending on the intended use.

Meanwhile, as a room temperature fast-curable organopolysiloxanecomposition of a condensation curing type, there have been known aone-solution type where a rate of crosslinking due to hydrolysis isimproved by using a curing agent on a base polymer which is anorganopolysiloxane having both terminal ends blocked by hydroxy groups;and a two-solution type where a base polymer which is anorganopolysiloxane having both terminal ends blocked by hydroxy groupsand a crosslinking agent are packed separately.

There have been known various room temperature-curable compositions thatcan be cured to form elastomers at room temperatures. Particularly, atype of composition that releases an alcohol(s) when being cured doesnot generate an unpleasant smell and cause metals to corrode. Therefore,such a type of composition is preferably used in sealing materials,adhesive agents and coating agents for electronic devices.

As such a type of composition, there have been disclosed a compositionconsisting of a polyorganosiloxane having its terminal ends blocked byhydroxyl groups, an alkoxysilane and an organic titanium compound; acomposition consisting of a polyorganosiloxane having its terminal endsblocked by alkoxysilyl groups, an alkoxysilane and an alkoxy titanium; acomposition consisting of a linear polyorganosiloxane having itsterminal ends blocked by alkoxysilyl groups and including a silethylenegroup(s), an alkoxysilane and an alkoxy titanium; and a compositionconsisting of a polyorganosiloxane having its terminal ends blocked byhydroxyl groups or a polyorganosiloxane having its terminal ends blockedby alkoxy groups and an alkoxy-α-silyl ester compound (Patent documents2 to 5).

Although these compositions are superior in preservation stability,water resistance and moisture resistance, they have exhibitedinsufficient fast curabilities.

As described above, a polymer having a reactive alkoxysilyl group at itsterminal ends is heretofore known. Since this polymer already has itspolymer terminal ends blocked by alkoxysilyl groups, there can beobtained a composition exhibiting a superior preservation stability anda curability that does not easily change (deteriorate) with time.Further, a workability (viscosity, thixotropy) thereof can bearbitrarily adjusted; there can be formed a cross-linkage and anelastomer thereof by reaction with the water in the air; and superiorproperties (hardness, tensile strength, elongation at break) can also beachieved.

However, since an alcohol-type curable composition has a low reactivitywith the water in the air as compared to heretofore known curablecompositions of other curing types such as an oxime-type, an aceticacid-type and an acetone-type, restrictions are imposed on locationswhere an alcohol-type curable composition can be used.

In response, studies have been made on a functional group (linkinggroup) adjacent to a reactive alkoxy group, and it has been reportedthat an α-alkoxysilylmethyl terminal end group is particularly highlyreactive with the water in the air (Patent document 6). However, thereexist downsides including a still insufficient curability; a negativeimpact inflicted on durability by the adjacent functional group (linkinggroup); and a low restorability of a cured product.

In addition, by attempting to solve the problem of the curability, therearises another problem where yellowing occurs after performing ananti-UV discoloration test.

PRIOR ART DOCUMENT Patent Documents

Patent document 1: Japanese Patent No. 3850969

Patent document 2: Japanese Examined Patent Application Publication No.Sho 39-27643

Patent document 3: JP-A-Sho 55-43119

Patent document 4: Japanese Examined Patent Application Publication No.Hei 7-39547

Patent document 5: JP-A-Hei 7-331076

Patent document 6: Japanese Unexamined Patent Application Publication(Translation of PCT Application) No. 2012-511607

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

The present invention was made in view of the aforementioned issues. Itis an object of the invention to provide a novel aluminum chelatecompound useful as, for example, a catalyst of a roomtemperature-curable resin; and a room temperature-curable resincomposition capable of forming a cured product not only superior in fastcurability, preservation stability and durability, but also superior inUV-discoloration resistance, such room temperature-curable resincomposition particularly being a room temperature-curableorganopolysiloxane composition.

Means to Solve the Problem

As a result of diligently conducting numerous studies to achieve theabovementioned objectives, the inventors of the present invention foundthat the aluminum chelate compound shown below was useful in solving theaforementioned problems. Moreover, the inventors found that there couldbe obtained a room temperature-curable composition capable of forming acured product superior in fast curability, preservation stability,durability and UV-discoloration resistance by using a polymer and/orcompound having an alkoxysilyl-ethylene group(s), where a linking groupadjacent to an alkoxysilyl group is an ethylene group; and by using analuminum chelate compound, particularly the following aluminum chelatecompound as a curing catalyst. In this way, the inventors completed thepresent invention.

That is, the present invention provides the following aluminum chelatecompound, room temperature-curable resin composition and the like.

<1> An aluminum chelate compound having a β-dicarbonyl compoundrepresented by the following general formula (1):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms; and A is a grouprepresented by the following formula (2) or a group represented by —OR⁸:

wherein each of R⁵ to R⁷ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R⁵ to R⁷ being either identical to or different from one another; and R⁸represents a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 5 carbon atoms), provided that an average coordinationnumber of the β-dicarbonyl compound represented by the general formula(1) to aluminum is 0.5 to 2.5.

<2> The aluminum chelate compound according to <1>, having a β-ketoesterrepresented by the following formula (3) and a diketone represented bythe following formula (4):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; and R⁸represents a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 5 carbon atoms)

(wherein each of R⁹ and R¹⁰ represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, R⁹ and R¹⁰being either identical to or different from each other; and R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms), provided that an averagemolecular coordination number of the β-ketoester represented by theformula (3) to aluminum is 0.5 to 2.5, an average molecular coordinationnumber of the diketone represented by the formula (4) to aluminum is 0.5to 2.5, and an average molecular coordination number of a total of theformulae (3) and (4) is 3.0.

<3> The aluminum chelate compound according to <1>, having a diketonerepresented by the following formula (5) and a β-ketoester representedby the following formula (6):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms; and each of R⁵ to R⁷represents a halogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms, R⁵ to R⁷ being eitheridentical to or different from one another)

(wherein R¹¹ represents a linear monovalent hydrocarbon group having 1to 12 carbon atoms; and R⁸ represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 5 carbon atoms), provided thatan average molecular coordination number of the diketone represented bythe formula (5) to aluminum is 0.5 to 2.5, an average molecularcoordination number of the β-ketoester represented by the formula (6) toaluminum is 0.5 to 2.5, and an average molecular coordination number ofa total of the formulae (5) and (6) is 3.0.

As for the aluminum chelate compounds of the present invention that aredefined above, an aggregate of aluminum chelate compounds belongs to thescope of the present invention as long as an average structure thereofas an aluminum chelate compound aggregate belongs to the scope shownabove, even when the aluminum chelate compounds differ from one anotherin structure.

<4> Further, the present invention also provides a curing catalyst of aresin containing the aforementioned aluminum chelate compound.

<5> A room temperature-curable resin composition including:

-   -   (A) 100 parts by mass of an alkoxysilyl-ethylene group        terminated polymer having in one molecule at least one structure        represented by the following general formula:

-   -   (wherein each of R¹ and R² represents a substituted or        unsubstituted monovalent hydrocarbon group having 1 to 12 carbon        atoms, R¹ and R² being either identical to or different from        each other; and a represents 2 or 3); and    -   (D) 0.001 to 15 parts by mass of an aluminum chelate compound.

<6> A room temperature-curable organopolysiloxane composition including:

-   -   (B) 100 parts by mass of a diorganopolysiloxane having in one        molecule at least two silicon atoms, each silicon atom being        bonded to a hydroxyl group and/or a hydrolyzable group;    -   (C) 0.1 to 30 parts by mass of an alkoxysilyl-ethylene        group-containing compound having in one molecule at least one        structure represented by the following general formula:

-   -   (wherein each of R¹ and R² represents a substituted or        unsubstituted monovalent hydrocarbon group having 1 to 12 carbon        atoms, R¹ and R² being either identical to or different from        each other; a represents 2 or 3; and n represents an integer of        0 to 10); and    -   (D) 0.001 to 15 parts by mass of an aluminum chelate compound.

<7> The room temperature-curable resin composition according to <5> or<6>, wherein the component (D) is the aluminum chelate compound as setforth in <1>, <2> or <3>.

<8> A molded product obtained by curing the room temperature-curableresin composition of any one of <5> to <7>.

<9> A coating, adhesive or sealing agent including the roomtemperature-curable resin composition of any one of <5> to <7>.

Effects of the Invention

The novel aluminum chelate compound of the present invention exhibits asuperior catalyst activity when used as a curing catalyst of a resin.This aluminum chelate compound is particularly useful as a curingcatalyst of a room temperature-curable resin.

Further, the room temperature-curable organopolysiloxane composition ofthe present invention is not only superior in heat resistance, waterresistance and moisture resistance, but also superior in fast curabilityand preservation stability. Particularly, this room temperature-curableorganopolysiloxane composition is capable of forming a cured productexhibiting a small degree of UV discoloration. For example, thecomposition of the present invention can be immediately cured whenexposed to the air, even after being stored for 12 months. Moreover,since there is no need to use a tin compound which is subject to controlin recent years, the composition of the present invention bears a lowenvironmental burden.

Therefore, the room temperature-curable organopolysiloxane compositionof the present invention is useful as a sealing material, a coatingagent and an adhesive agent that are applied in locations requiring aheat resistance, a water resistance and a moisture resistance.Particularly, this room temperature-curable organopolysiloxanecomposition is useful as an adhesive agent for architecture purpose; andelectrical and electronic purpose, where a steam resistance and waterresistance are required.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹HNMR chart of an aluminum chelate compound obtained in afirst working example.

FIG. 2 is a ¹HNMR chart of an aluminum chelate compound obtained in asecond working example.

FIG. 3 is a ¹HNMR chart of an aluminum chelate compound obtained in athird working example.

MODE FOR CARRYING OUT THE INVENTION <Aluminum Chelate Compound>

The aforementioned aluminum chelate compound of the present invention isa compound suitable as a curing agent of a room temperature-curableresin.

Here, in the above general formulas (1) and (2), substituted orunsubstituted monovalent hydrocarbon groups each having 1 to 12 carbonatoms, which are represented by R¹ to R⁷, can be either linear, cyclicor branched. Examples of such monovalent hydrocarbon group include alinear alkyl group such as a methyl group, an ethyl group, a propylgroup, an n-butyl group, a hexyl group, a heptyl group, an octyl group,a nonyl group and a decyl group; a cyclic alkyl group such as acyclohexyl group; a branched alkyl group such as an t-butyl group and a2-ethylhexyl group; and a substituted group e.g. a halogen-substitutedmonovalent hydrocarbon group such as a trifluoromethyl group, abromoethyl group and a trichloropropyl group that are obtained bysubstituting a part or all of the hydrogen atoms of the aforementionedlinear, cyclic or branched alkyl groups with a halogen atom(s) such as achlorine, a fluorine and a bromine atom(s). Examples of such halogenatoms include chlorine, fluorine and bromine atoms. These groups may beeither identical to or different from one another. It is preferred thateach of R¹ to R³ and R⁵ to R⁸ of the present invention be a methylgroup, an ethyl group or a fluorine atom. Particularly, it is preferredthat R⁴ be either a hydrogen atom or a methyl group.

Here, in the above general formula (3), substituted or unsubstitutedmonovalent hydrocarbon groups each having 1 to 12 carbon atoms, whichare represented by R¹ to R³, can be either linear, cyclic or branched.Examples of such monovalent hydrocarbon group include a linear alkylgroup such as a methyl group, an ethyl group, a propyl group, an n-butylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group anda decyl group; a cyclic alkyl group such as a cyclohexyl group; abranched alkyl group such as an t-butyl group and a 2-ethylhexyl group;and a substituted group e.g. a halogen-substituted monovalenthydrocarbon group such as a trifluoromethyl group, a bromoethyl groupand a trichloropropyl group that are obtained by substituting a part orall of the hydrogen atoms of the aforementioned linear, cyclic orbranched alkyl groups with a halogen atom(s) such as a chlorine, afluorine and a bromine atom(s). Examples of such halogen atoms includechlorine, fluorine and bromine atoms. These groups may be eitheridentical to or different from one another. A substituted orunsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms,which is represented by R⁸, can be either linear, cyclic or branched.Examples of this monovalent hydrocarbon group include a linear alkylgroup such as a methyl group, an ethyl group, a propyl group and ann-butyl group; a cyclic alkyl group such as a cyclopentyl group; abranched alkyl group such as a t-butyl group; and a substituted groupe.g. a halogen-substituted monovalent hydrocarbon group such as atrifluoromethyl group, a bromoethyl group and a trichloropropyl groupthat are obtained by substituting a part or all of the hydrogen atoms ofthe aforementioned linear, cyclic or branched alkyl groups with ahalogen atom(s) such as a chlorine, a fluorine and a bromine atom(s). Itis preferred that each of R¹ to R³ of the present invention be a methylgroup and/or a fluorine atom. Particularly, it is preferred that R⁸ be amethyl group and/or an ethyl group.

Here, in the above general formula (4), substituted or unsubstitutedmonovalent hydrocarbon groups each having 1 to 12 carbon atoms, whichare represented by R⁴, R⁹ and R¹⁰, can be either linear, cyclic orbranched. Examples of such monovalent hydrocarbon group include a linearalkyl group such as a methyl group, an ethyl group, a propyl group, ann-butyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup and a decyl group; a cyclic alkyl group such as a cyclohexylgroup; a branched alkyl group such as a t-butyl group and a 2-ethylhexylgroup; and a substituted group e.g. a halogen-substituted monovalenthydrocarbon group such as a trifluoromethyl group, a bromoethyl groupand a trichloropropyl group that are obtained by substituting a part orall of the hydrogen atoms of the aforementioned linear, cyclic orbranched alkyl groups with a halogen atom(s) such as a chlorine, afluorine and a bromine atom(s). These groups may be either identical toor different from one another. It is preferred that R⁹ and R¹⁰ of thepresent invention be a methyl group and/or an ethyl group. Particularly,it is preferred that R⁴ be a hydrogen atom and/or a methyl group.

Here, in the above general formula (5), substituted or unsubstitutedmonovalent hydrocarbon groups each having 1 to 12 carbon atoms, whichare represented by R¹ to R⁷, can be either linear, cyclic or branched.Examples of such monovalent hydrocarbon group include a linear alkylgroup such as a methyl group, an ethyl group, a propyl group, an n-butylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group anda decyl group; a cyclic alkyl group such as a cyclohexyl group; abranched alkyl group such as a t-butyl group and a 2-ethylhexyl group;and a substituted group e.g. a halogen-substituted monovalenthydrocarbon group such as a trifluoromethyl group, a bromoethyl groupand a trichloropropyl group that are obtained by substituting a part orall of the hydrogen atoms of the aforementioned linear, cyclic orbranched alkyl groups with a halogen atom(s) such as a chlorine, afluorine and a bromine atom(s). These groups may be either identical toor different from one another. It is preferred that each of R¹ to R³ andR⁵ to R⁷ of the present invention be a methyl group and/or an ethylgroup. Particularly, it is preferred that R⁴ be a hydrogen atom and/or amethyl group.

Here, in the above general formula (6), an unsubstituted monovalentlinear hydrocarbon group having 1 to 12 carbon atoms, which isrepresented by R¹¹, can be, for example, a linear alkyl group such as amethyl group, an ethyl group, a propyl group, an n-butyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group and a decyl group.A substituted or unsubstituted monovalent hydrocarbon group having 1 to5 carbon atoms, which is represented by R⁸, can be either linear, cyclicor branched. Examples of such monovalent hydrocarbon group include alinear alkyl group such as a methyl group, an ethyl group, a propylgroup and an n-butyl group; a cyclic alkyl group such as a cyclopentylgroup; a branched alkyl group such as a t-butyl group; and a substitutedgroup e.g. a halogen-substituted monovalent hydrocarbon group such as atrifluoromethyl group, a bromoethyl group and a trichloropropyl groupthat are obtained by substituting a part or all of the hydrogen atoms ofthe aforementioned linear, cyclic or branched alkyl groups with ahalogen atom(s) such as a chlorine, a fluorine and a bromine atom(s). Itis preferred that R¹¹ of the present invention be a methyl group and/oran ethyl group. Particularly, it is preferred that R⁸ be a methyl groupand/or an ethyl group.

The aluminum chelate derivative of the present invention can, forexample, be produced through the following method. That is, aluminumalkoxide is to be dissolved in an appropriate solvent such as toluene,followed by delivering β-ketoester and then β-diketone by drops intosuch solution before stirring the same at a room temperature. Later, byremoving the solvent and/or alcohol from such reaction solution, therecan be produced the target aluminum chelate compound.

<Room Temperature-Curable Resin Composition> [Component (A)]

In the present invention, a component (A) is an alkoxysilyl-ethylenegroup terminated polymer having at least one structure represented bythe following general formula in one molecule

(in the above formula, each of R¹ and R² is a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms.R¹ and R² may be identical to or different from each other, and arepresents either 2 or 3.)

In the above formula, examples of the substituted or unsubstitutedmonovalent hydrocarbon group represented by R¹ and R² include an alkylgroup such as a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group and an octadecyl group; a cycloalkyl groupsuch as a cyclopentyl group and a cyclohexyl group; an alkenyl groupsuch as a vinyl group, an allyl group, a butenyl group, a pentenyl groupand a hexenyl group; an aryl group such as a phenyl group, a tolylgroup, a xylyl group and an α-naphthyl group, β-naphthyl group; anaralkyl group such as a benzyl group, a 2-phenylethyl group and a3-phenylpropyl group; and substituted groups obtained by substituting apart or all of the hydrogen atoms of any of the abovementioned groupswith halogen atoms such as F, Cl and Br or with cyano groups or thelike, such substituted groups including a 3-chloropropyl group, a3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like. Amongthese groups, a methyl group and an ethyl group are preferred, and amethyl group is particularly preferred.

Examples of a hydrolyzable group (R¹O—) at the terminal end(s) of amolecular chain include an alkoxy group such as a methoxy group, anethoxy group, a propoxy group and a 2-ethylhexoxy group; and analkoxyalkoxy group such as a methoxyethoxy group, an ethoxyethoxy groupand a methoxypropoxy group. Among these groups, a methoxy group and anethoxy group are particularly preferred because of their fastcurabilities.

The component (A) is used as a main agent (base polymer) of thecomposition, and may be either linear or branched. The aforementionedpolymer may be composed of various units such as polysiloxane,polyether, polyurethane, polyurea, polyester, polysiloxane-urea/urethanecopolymer, polyacrylate, polymethacrylate, polycarbonate, polystyrene,polyamide, polyvinyl ester, polyolefin, polyethylene, polybutadiene,ethylene-olefin copolymer, and styrene-butadiene copolymer. An arbitrarymixture or combination of these polymers can also be used.

Especially, a polysiloxane having an alkoxysilyl-ethylene group at itsterminal end(s) is a novel compound that is superior in durability andcan be used favorably. Specific examples of such polysiloxane includethe diorganopolysiloxane represented by the following general formulas(12) and/or (13).

(in the above formulas, each of R¹ and R² represents a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms;a represents 2 or 3; m represents an integer of 1 to 10; n represents anumber by which the diorganopolysiloxane exhibits a viscosity of 10 to1,000,000 mPa·s at 25° C.)

In the above formulas, examples of the substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, which isrepresented by R¹ and R², include an alkyl group such as a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group andan octadecyl group; a cycloalkyl group such as a cyclopentyl group and acyclohexyl group; an alkenyl group such as a vinyl group, an allylgroup, a butenyl group, a pentenyl group and a hexenyl group; an arylgroup such as a phenyl group, a tolyl group, a xylyl group and an α-,β-naphthyl group; an aralkyl group such as a benzyl group, a2-phenylethyl group and a 3-phenylpropyl group; and substituted groupsobtained by substituting a part or all of the hydrogen atoms of any ofthe abovementioned groups with halogen atoms such as F, Cl and Br orwith cyano groups or the like, such substituted groups including a3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethylgroup and the like. Among these groups, a methyl group and an ethylgroup are preferred, and a methyl group is particularly preferred.

Examples of a hydrolyzable group (R¹O—) at the terminal end(s) of amolecular chain include an alkoxy group such as a methoxy group, anethoxy group, a propoxy group and a 2-ethylhexoxy group; and analkoxyalkoxy group such as a methoxyethoxy group, an ethoxyethoxy groupand a methoxypropoxy group. Among these groups, a methoxy group and anethoxy group are particularly preferred because of their fastcurabilities.

At the temperature of 25° C., it is preferred that the polymer as thecomponent (A) exhibit a viscosity of 10 to 1,000,000 mPa·s, morepreferably 50 to 500,000 mPa·s, particularly preferably 100 to 100,000mPa·s, especially preferably 100 to 80,000 mPa·s. It is preferable whenthe viscosity of the diorganopolysiloxane is not lower than 10 mPa·s,because there can be easily obtained a coating film superior in physicaland mechanical strengths in such case. It is also preferable when suchviscosity is not higher than 1,000,000 mPa·s, because the viscosity ofthe composition will not be become excessively high in such case so thata favorable workability can be achieved at the point of use. Here, theviscosity refers to a value measured by a rotary viscometer.

The polymer as the component (A) can be produced as follows. Forexample, a diorganopolysiloxane having ethynyl groups at both of itsterminal ends is first produced by a polymerization reaction between adisiloxane having acetylene groups at both of its terminal ends and anoctamethylcyclotetrasiloxane under the presence of a sulfuric acid.Next, a trialkoxysilane is added thereto to obtain the polymer as thecomponent (A).

As a catalyst for addition reaction used here, there can be employed aplatinum group metal based catalyst such as a platinum based catalyst, apalladium based catalyst and a rhodium based catalyst, among which aplatinum based catalyst is particularly preferred. Examples of suchplatinum based catalyst include catalysts with a solid platinum beingsupported on a support such as platinum black, alumina or silica; achloroplatinic acid; an alcohol-modified chloroplatinic acid; a complexof a chloroplatinic acid and olefin; or a complex of platinum and vinylsiloxane. The amount of these catalysts used may be a so-calledcatalytic amount. These catalysts can be used in an amount of 0.1 to1,000 ppm, particularly 0.5 to 100 ppm with respect to, for example,trialkoxysilanes, in terms of platinum group metal.

It is desired that this reaction be normally performed at a temperatureof 50 to 120° C., particularly 60 to 100° C., for 0.5 to 12 hours,particularly 1 to 6 hours. Further, although this reaction may beperformed without using a solvent, there can be employed an appropriatesolvent such as toluene and xylene if necessary, provided that therewill be no adverse impact on the aforementioned addition reaction or thelike.

In an addition reaction to an acetylene group(s), a geometric isomerrepresented by the following formula (14) is formed. Trans-isomers arerichly produced and highly reactive in the geometric isomers. And, it isnot required that trans-isomers and cis-isomers be separated when usingthe diorganopolysiloxane of the present invention because of no adverseimpact on the properties of the diorganopolysiloxane.

Specific examples of the diorganopolysiloxane as the component (A) areas follows.

(in the above formulas, the definitions of m, n, R¹ and R² are identicalto those of the component (A).)

As for the diorganopolysiloxane as the component (A), there may be usedeither one kind thereof; or not less than two kinds thereof withdiffering structures and molecular weights.

[Component (B)]

A diorganopolysiloxane as a component (B) is a main agent (base polymer)of the room temperature-curable organopolysiloxane composition of thepresent invention. The diorganopolysiloxane as the component (B) has atleast two hydroxyl groups or hydrolyzable groups that are bonded tosilicone atoms, in each molecule. Specific examples of suchdiorganopolysiloxane include the following diorganopolysiloxanes withthe terminal ends of their molecular chains being blocked by hydroxylgroups or hydrolyzable groups, as represented by the general formulas(15) and (16) below.

(in the above formula, R represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12, preferably 1 to 8 carbonatoms; X represents a bivalent hydrocarbon group having 1 to 8,preferably 1 to 6 oxygen or carbon atoms; Y represents a hydrolyzablegroup; b represents 2 or 3; m represents a number by which thisdiorganopolysiloxane exhibits a viscosity of 100 to 1,000,000 mPa·s at25° C.)

In the above formula, examples of the substituted or unsubstitutedmonovalent hydrocarbon group represented by R include an alkyl groupsuch as a methyl group, an ethyl group, a propyl group, a butyl group, apentyl group, an hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group and an octadecyl group; a cycloalkyl group such asa cyclopentyl group and a cyclohexyl group; an alkenyl group such as avinyl group, an allyl group, a butenyl group, a pentenyl group and ahexenyl group; an aryl group such as a phenyl group, a tolyl group, axylyl group and an α-naphthyl group, β-naphthyl group; an aralkyl groupsuch as a benzyl group, a 2-phenylethyl group and a 3-phenylpropylgroup; and substituted groups obtained by substituting a part or all ofthe hydrogen atoms of any of the abovementioned groups with halogenatoms such as F, Cl and Br or with cyano groups or the like, suchsubstituted groups including a 3-chloropropyl group, a3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like. Amongthese groups, a methyl group, an ethyl group and a phenyl group arepreferred, and a methyl group is particularly preferred.

X represents a bivalent hydrocarbon group having 1 to 8 oxygen or carbonatoms. It is preferred that X as a bivalent hydrocarbon group berepresented by —(CH₂)_(p)— (p represents an integer of 1 to 8), amongwhich an oxygen atom and —CH₂CH₂— are preferred.

Y represents a hydrolyzable group at the terminal ends of the molecularchain of the aforementioned diorganopolysiloxane. Examples of suchhydrolyzable group include an alkoxy group such as a methoxy group, anethoxy group and a propoxy group; an alkoxyalkoxy group such as amethoxyethoxy group, an ethoxyethoxy group and a methoxypropoxy group;an acyloxy group such as an acetoxy group, an octanoyloxy group and abenzoyloxy group; an alkenyloxy group such as a vinyloxy group, anisopropenyloxy group and a 1-ethyl-2-methylvinyloxy group; a ketoximegroup such as a dimethylketoxime group, an methylethyl ketoxime groupand a diethylketoxime group; an amino group such as a dimethylaminogroup, a diethylamino group, a butylamino group and a cyclohexylaminogroup; an aminoxy group such as a dimethylaminoxy group and adiethylaminoxy group; and an amide group such as an N-methylacetamidegroup, an N-ethylacetamide group and an N-methylbenzamide group. Amongthese groups, an alkoxy group is preferred, a methoxy group and anethoxy group are more preferred, and a methoxy group is particularlypreferred.

At the temperature of 25° C., it is preferred that thediorganopolysiloxane as the component (B) exhibit a viscosity of 100 to1,000,000 mPa·s, more preferably 300 to 500,000 mPa·s, particularlypreferably 500 to 100,000 mPa·s, especially 1,000 to 80,000 mPa·s. Whenthe viscosity of such diorganopolysiloxane is lower than 100 mPa·s, itmay be difficult to obtain a cured product superior in physical andmechanical strengths. A viscosity greater than 1,000,000 mPa·s leads toan excessively high viscosity of the composition such that anunfavorable workability will be resulted at the point of use. Here, suchviscosity is a value measured by a rotary viscometer.

Specific examples of the diorganopolysiloxane as the component (B)include those represented by the following formulas.

(in the above formulas, the definitions of m, R and Y are identical tothose of the component (B); b′ represents 0 or 1.)

As for the diorganopolysiloxane as the component (B), there may be usedeither one kind thereof; or not less than two kinds thereof withdiffering structures and degrees of polymerization.

[Component (C)]

A component (C) is an alkoxysilyl-ethylene group-containing compoundhaving at least one structure represented by the following formula inone molecule. The component (C) serves as a cross-linking agent of thecomponent (B).

(in the above formula, each of R¹ and R² represents a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms;R¹ and R² may be identical to or different from each other; a represents2 or 3; n represents an integer of 0 to 10.)

A compound having the aforementioned structure can, for example, beobtained by adding a silane having an acetylene group(s) and atrialkoxysilane.

As a catalyst for addition reaction used here, there can be employed aplatinum group metal based catalyst such as a platinum based catalyst, apalladium based catalyst and a rhodium based catalyst, among which aplatinum based catalyst is particularly preferred. Examples of suchplatinum based catalyst include catalysts with a solid platinum beingsupported on a support such as platinum black, alumina or silica; achloroplatinic acid; an alcohol-modified chloroplatinic acid; a complexof a chloroplatinic acid and olefin; or a complex of platinum and vinylsiloxane. The amount of these catalysts used may be a so-calledcatalytic amount. These catalysts can be used in an amount of 0.1 to1,000 ppm, particularly 0.5 to 100 ppm with respect to, for example,trialkoxysilanes, in terms of platinum group metal.

It is desired that this reaction be normally performed at a temperatureof 50 to 120° C., particularly 60 to 100° C., for 0.5 to 12 hours,particularly 1 to 6 hours. Further, although this reaction may beperformed without using a solvent, there can be employed an appropriatesolvent such as toluene and xylene if necessary, provided that therewill be no adverse impact on the aforementioned addition reaction or thelike.

In an addition reaction to an acetylene group(s), a geometric isomerrepresented by the following formula is formed. Because trans-isomersare richly produced and highly reactive in the geometric isomers, it ispreferable that the component (C) of the present invention containingthe trans-isomer is used.

It is preferred that the component (C) such as those described above beadded in an amount of 0.1 to 30 parts by mass, particularly 0.5 to 20parts by mass with respect to 100 parts by mass of theorganopolysiloxane as the component (B).

Specific examples of the component (C) include those represented by thefollowing formulas.

[Component (D)]

An aluminum chelate compound as a component (D) is a curing catalyst anda critical component for obtaining the invention of the presentapplication. Examples of the aluminum chelate compound as the component(D) include those described above.

As for such aluminum chelate compound as the component (D), there may beused either one kind thereof; or not less than two kinds thereof in amixed manner.

It is preferred that the component (D) be added in an amount of 0.001 to15 parts by mass, particularly 0.005 to 10 parts by mass with respect to100 parts by mass of the component (A) or the component (B).

As for the room temperature curable-organopolysiloxane composition ofthe present invention, the following optional components may be addedthereto.

[Component (E)]

A component (E) is a silane and/or its partial hydrolysis condensation,serving as a cross-linking agent other than the component (C). Specificexamples of such component (E) include ethyl silicate, propyl silicate,methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris(methoxyethoxy) silane and methyltripropenoxysilane; as well as partialhydrolysis condensation thereof. Not only one kind, but two or morekinds of such compositions can be used in combination.

The component (E) is normally added in an amount of 0 to 30 parts bymass with respect to 100 parts by mass of the component (A) or thecomponent (B). However, it is preferred that the component (E) be addedin an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 15 partsby mass with respect to 100 parts by mass of the component (A) or thecomponent (B). When the amount of the component (E) added is greaterthan 30 parts by mass, there occurs a problem where the cured producthardens in an excessive manner such that an economic disadvantage isresulted.

[Component (F)]

A component (F) is a filler and is used to endow the cured productformed of such composition with a sufficient mechanical strength. Whileknown materials can be used as such filler, examples of this fillerinclude a metal oxide such as a fine powder silica, an aerosol silica, asilica aerogel, a precipitated silica, a diatom earth, an iron oxide, azinc oxide and a titanium oxide; any of these metal oxidessurface-treated with silane; a metal carbonate such as a calciumcarbonate, a magnesium carbonate and a zinc carbonate; asbestos; a glasswool; carbon black; a fine powder mica; a molten silica powder; and asynthesized resin powder such as that of polystyrene, polyvinyl chlorideor polypropylene.

The component (F) is added in an amount of 0 to 1,000 parts by mass withrespect to 100 parts by mass of the component (A) or the component (B).Particularly, it is preferred that the component (F) be added in anamount of 1 to 400 parts by mass with respect to 100 parts by mass ofthe component (A) or the component (B). When the amount of the component(F) added is greater than 1,000 parts by mass, not only the workabilitywill be impaired due to an increased viscosity of the composition, butit will also be difficult to achieve a rubber elasticity as a rubberstrength decreases after curing. When the component (F) is added in anamount of not smaller than 1 part by mass, the mechanical strength ofthe cured product obtained can be improved sufficiently.

[Component (G)]

A component (G) is an adhesion aid and is used to endow the curedproduct made from this composition with a sufficient adhesiveness.

As such component (G), particularly preferred are aminosilanes such asγ-aminopropyltriethoxysilane and 3-2-(aminoethylamino)propyltrimethoxysilane; epoxysilanes such asγ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanate silane and the like.

It is preferred that the component (G) be added in an amount of 0 to 30parts by mass, particularly 0.1 to 20 parts by mass with respect to 100parts by mass of the components (A) and (B).

Further, heretofore known additives may be added to the roomtemperature-curable organopolysiloxane composition of the presentinvention. Examples of such additives include a pigment; a dye; ananti-aging agent; an antioxidant; an antistatic agent; and a flameretardant such as antimony oxide and chlorinated paraffin. Furthermore,as a thixotropy improver, there can be added a polyether, a fungicide oran antimicrobial agent.

In fact, the room temperature-curable organopolysiloxane composition ofthe present invention can be obtained by uniformly mixing together theaforementioned components and the aforementioned various additives by aparticular amount(s) in a dry atmosphere.

Here, the room temperature-curable organopolysiloxane composition can becured when left at a room temperature. However, as for a forming methodas well as a curing condition(s) thereof, there may be employedheretofore known methods and conditions in accordance with the types ofthe compositions.

The room temperature-curable organopolysiloxane composition of thepresent invention thus obtained can be rapidly cured at a roomtemperature by moisture in the air, thereby forming a rubber elasticbody cured product superior in heat resistance, weather resistance,low-temperature property and adhesiveness to various base materials,especially metals. Further, this composition is particularly superior inpreservation stability and curability. For example, the composition iscapable of being rapidly cured when exposed to the air even after beingstored for 6 months, thus forming a cured product having theabovementioned superior properties. Particularly, no toxic or corrosivegas will be emitted at the time of curing such that no rust will occuron a surface treated with such composition. More particularly, sincethis composition does not cause contact faults among electric/electronicparts, not only it is useful as an insulating material forelectric/electronic parts or as an adhesive agent, but the compositionmay also be widely used as a sealing agent, a coating agent, a coveringagent, a mold-releasing treating agent or even a textile treating agentfor various base materials. Further, this composition can be cured andformed into various molded products that are superior in heatresistance, weather resistance and the like.

WORKING EXAMPLE

Next, working and comparative examples are shown to describe the presentinvention in detail. However, the present invention is not limited tothe following working examples.

Working Example 1

Aluminum triethoxide of 0.81 g (5.0 mmol) and toluene of 2.0 ml wereplaced in a 50 ml eggplant-shaped flask, followed by deliveringthereinto 1.58 g (10.0 mmol) of 4,4-dimethyl-3-oxopentanoic acid methyland then 0.50 g (5.0 mmol) of 2,4-pentanedione by drops while performingstirring. After performing stirring under a room temperature for 24hours, the ethanol generated was then distilled to obtain 2.20 g (yield100%) of a yellow viscous fluid having an average structure of that of amonoacetylacetonate aluminum bis (methylpivaloylacetoacetate) chelate.

A measurement through ¹H-NMR spectrum was performed (FIG. 1) to confirmthe average structure of the product generated.

¹H-NMR spectrum:

δ 0.91 to 0.98 ppm (ratio of H: 6, —C(O)—C(CH₃)₃)

1.84 to 1.92 ppm (ratio of H: 6, —C(O)—CH₃)

4.11 to 4.18 ppm (ratio of H: 6, —OCH₃)

4.90 to 5.40 ppm (ratio of H: 3, —C(O)CHC(O)—)

According to the results of the measurement through ¹H-NMR spectrum, itis regarded that the product obtained has the average structure of amonoacetylacetonate aluminum bis (methylpivaloylacetoacetate) chelaterepresented by the structure of the formula (7).

Working Example 2

Aluminum triethoxide of 0.81 g (5.0 mmol) and toluene of 2.0 ml wereplaced in a 50 ml eggplant-shaped flask, followed by deliveringthereinto 1.84 g (10.0 mmol) of 4,4,4-ethyl trifluoroacetoacetate andthen 0.50 g (5.0 mmol) of 2,4-pentanedione by drops while performingstirring. After performing stirring under a room temperature for 24hours, the ethanol generated was then distilled to obtain 2.46 g (yield100%) of a yellow viscous fluid having an average structure of that of amonoacetylacetonate aluminum bis (ethyl-4,4,4-trifluoroacetoacetate)chelate.

A measurement through ¹H-NMR spectrum was performed (FIG. 2) to confirmthe average structure of the product generated.

¹H-NMR spectrum:

δ 1.17 to 1.21 ppm (ratio of H: 6, —OCH₂CH₃)

1.89 to 1.93 ppm (ratio of H: 6, —C(O)—CH₃)

4.11 to 4.18 ppm (ratio of H: 4, —OCH₂CH₃)

5.29 to 5.43 ppm (ratio of H: 3, —C(O)CHC(O)—)

According to the results of the measurement through ¹H-NMR spectrum, itis regarded that the product obtained has the average structure of amonoacetylacetonate aluminum bis (ethyl-4,4,4-trifluoroacetoacetate)chelate represented by the structure of the formula (8).

Working Example 3

Aluminum triethoxide of 0.81 g (5.0 mmol) and toluene of 2.0 ml wereplaced in a 50 ml eggplant-shaped flask, followed by deliveringthereinto 1.30 g (10.0 mmol) of ethyl acetoacetate and then 0.92 g (5.0mmol) of dipivaloylmethane by drops while performing stirring. Afterperforming stirring under a room temperature for 24 hours, the ethanoland toluene generated were then distilled to obtain 2.34 g (yield 100%)of a yellow viscous fluid having an average structure of that of a mono(dipivaloylmethane) aluminum bis (ethylacetoacetate) chelate.

A measurement through ¹H-NMR spectrum was performed (FIG. 3) to confirmthe average structure of the product generated.

¹H-NMR spectrum:

δ 0.91 to 1.04 ppm (ratio of H: 6, —OCH₂CH₃)

1.16 to 1.24 ppm (ratio of H: 18, —C(O)—C(CH₃)₃)

1.82 to 1.86 ppm (ratio of H: 6, —C(O)—CH₃)

3.96 to 4.11 ppm (ratio of H 4, —OCH₂CH₃)

5.18 to 5.90 ppm (ratio of H 3, —C(O) CHC(O)—)

According to the results of the measurement through ¹H-NMR spectrum, itis regarded that the product obtained has the average structure of amono (dipivaloylmethane) aluminum bis (ethylacetoacetate) chelaterepresented by the structure of the formula (9).

Working Example 4

A composition was obtained by mixing together 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by trimethoxysilyl-ethylene groups and exhibiting a viscosity of970 mPa·s; and 0.5 parts of the monoacetylacetonate aluminum bis(methylpivaloylacetoacetate) chelate prepared in the working example 1,in an environment where moisture was blocked, until a uniformconsistency was achieved. Each freshly obtained composition was thenpushed out on a glass Petri dish, and then exposed to an air of 50% RHat 23° C. The hardness of a cured product obtained after leaving thecomposition in such manner for 24 hours, was then measured using ahardness meter, a durometer A in compliance with JIS K-6249.

Working Example 5

A composition was obtained by mixing together 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by trimethoxysilyl-ethylene groups and exhibiting a viscosity of970 mPa·s; and 0.5 parts of the monoacetylacetonate aluminum bis(ethyl-4,4,4-trifluoroacetoacetate) chelate prepared in the workingexample 2, in an environment where moisture was blocked, until a uniformconsistency was achieved. Each freshly obtained composition was thenpushed out on a glass Petri dish, and then exposed to an air of 50% RHat 23° C. The hardness of a cured product obtained after leaving thecomposition in such manner for 24 hours, was then measured using ahardness meter, a durometer A in compliance with JIS K-6249.

Working Example 6

A composition was obtained by mixing together 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by trimethoxysilyl-ethylene groups and exhibiting a viscosity of970 mPa·s; and 0.5 parts of the monoacetylacetonate aluminum bis(methylpivaloylacetoacetate) chelate prepared in the working example 3,in an environment where moisture was blocked, until a uniformconsistency was achieved. Each freshly obtained composition was thenpushed out on a glass Petri dish, and then exposed to an air of 50% RHat 23° C. The hardness of a cured product obtained after leaving thecomposition in such manner for 24 hours, was then measured using ahardness meter, a durometer A in compliance with JIS K-6249.

Working Examples 7 to 9

Compositions were obtained in the same manner as that of the workingexamples 4 to 6 except that there was employed 100 parts of adimethylpolysiloxane having terminal ends of its branched chain blockedby trimethoxysilyl-ethane groups, instead of 100 parts of adimethylpolysiloxane having terminal ends of its molecular chain blockedby trimethoxysilyl-ethylene groups.

Comparative Examples 1 and 2

Compositions were obtained in the same manner as that of the workingexample 4 except that 0.5 parts of a monoacetylacetonate aluminum bis(ethylacetoacetate) 76% isopropanol solution (product name: AluminumChelate D by Kawaken Fine Chemicals Co., Ltd.) or a monoacetylacetonatealuminum bis (2-ethylhexylacetoacetate), instead of 0.5 parts of thealuminum chelate compound synthesized in the working example 1.

Comparative Examples 3 and 4

Compositions were obtained in the same manner as that of the workingexample 7 except that 0.5 parts of a monoacetylacetonate aluminum bis(ethylacetoacetate) 76% isopropanol solution (product name: AluminumChelate D by Kawaken Fine Chemicals Co., Ltd.) or a monoacetylacetonatealuminum bis (2-ethylhexylacetoacetate), instead of 0.5 parts of thealuminum chelate compound synthesized in the working example 1.

These results are shown in Table 1.

TABLE 1 Working Comparative Working Comparative example example exampleexample 4 5 6 1 2 7 8 9 3 4 Aluminum Working example 1 0.5 0.5 chelateWorking example 2 0.5 0.5 compound Working example 3 0.5 0.5 Aluminumchelate D 0.5 0.5 Ethylhexyl 0.5 0.5 Dimethyl Ethylene bridge 100 100100 100 100 polysiloxane Ethane bridge 100 100 100 100 100 Curability ◯◯ ◯ ◯ ◯ ◯ ◯ ◯ X X Hardness/Duro.A 17 15 24 13 4 6 1 11 — —

According to the results shown in Table 1, it is obvious that each ofthe aluminum chelate compounds described in the working examples 1 to 3has a curability higher than those of the correspondingmonoacetylacetonate aluminum bis (ethylacetoacetate) 76% isopropanolsolution (product name: Aluminum Chelate D by Kawaken Fine ChemicalsCo., Ltd.) and monoacetylacetonate aluminum bis(2-ethylhexylacetoacetate) as listed as an example in the publication ofJapanese Patent No. 3850969.

As for the room temperature-curable resin composition, working andcomparative examples are shown below to describe the present inventionin detail. However, the present invention is not limited to thefollowing working examples. In the following specific examples, “parts”refers to “parts by mass,” and a viscosity refers to a value measured bya rotary viscometer at 25° C.

SYNTHESIS EXAMPLE Synthesis Example 1

Following is a method for synthesizing the dimethylpolysiloxane compoundused in the working examples and having both terminal ends blocked bytrimethoxysilyl-ethylene groups.

<Synthesis of Dimethylpolysiloxane Compound Having Ethynyl Groups atBoth Terminal Ends>

Octamethylcyclotetrasiloxane of 3,050 g,1,3-diethynyl-1,1,3,3-tetramethyldisiloxane of 32 g and a concentratedsulfuric acid (H₂SO₄) of 154 g were put in a 5,000 mL four-neckedseparable flask equipped with a mechanical stirrer, a thermometer and adropping funnel. These ingredients were then stirred together at a roomtemperature (23° C.) for not less than 3 hours. Later, water (H₂O) of 66g was added thereto, and the ingredients were further stirred togetherfor not less than an hour. Next, toluene of 500 mL was added thereto toperform an isolation or separation of waste acid, and the toluenesolution was later subjected to water washing until it had becomeneutral. The following polymer A exhibiting a viscosity of 935 mPa·s wasobtained by stripping toluene and low molecular siloxane under a reducedpressure-condition of 150° C./8 mmHg.

<Synthesis of Dimethylpolysiloxane Compound Having Both Terminal EndsBlocked by Trimethoxysilyl-Ethylene Groups>

The polymer A of 1,000 g, trimethoxysilane of 6.4 g and a chloroplatinicacid (H₂PtCl₆.6H₂O) of 0.5 g were placed in a 5,000 mL four-neckedseparable flask equipped with a mechanical stirrer, a thermometer and adropping funnel. These ingredients were then stirred together at 70° C.for 3 hours. Later, the following polymer B exhibiting a viscosity of970 mPa·s was obtained by performing stripping under a reducedpressure-condition of 120° C./20 mmHg.

Working Example 10

A composition was obtained by mixing together 100 parts of adimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 0.5 parts of themonoacetylacetonate aluminum bis (ethylacetoacetate) 76% isopropanolsolution (product name: Aluminum Chelate D by Kawaken Fine ChemicalsCo., Ltd.), in an environment where moisture was blocked, until auniform consistency was achieved.

Working Example 11

A composition was obtained by mixing together 100 parts of thedimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 0.5 parts of themonoacetylacetonate aluminum bis (ethyl-4,4,4-trifluoroacetoacetate)chelate prepared in the working example 2, in an environment wheremoisture was blocked, until a uniform consistency was achieved.

Working Example 12

A composition was obtained by mixing together 100 parts of thedimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 0.5 parts of themonoacetylacetonate aluminum bis (methylpivaloylacetoacetate) chelateprepared in the working example 1, in an environment where moisture wasblocked, until a uniform consistency was achieved.

Working Example 13

A composition was obtained by mixing together 100 parts of thedimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 0.5 parts of the mono(dipivaloylmethane) aluminum bis (ethylacetoacetate) chelate prepared inthe working example 3, in an environment where moisture was blocked,until a uniform consistency was achieved.

Working Example 14

A composition was obtained by mixing together 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by hydroxyl groups and exhibiting a viscosity of 700 mPa·s; 6parts of the following compound; and 0.5 parts of themonoacetylacetonate aluminum bis (methylpivaloylacetoacetate) chelate,in an environment where moisture was blocked, until a uniformconsistency was achieved.

Comparative Examples 5 to 8

Compositions were obtained in the same manner as that of the workingexamples 10 to 13 except that there was used 100 parts of adimethylpolysiloxane having the terminal ends of its molecular chainblocked by trimethoxysilyl-ethane groups, instead of 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by trimethoxysilyl-ethylene groups.

Comparative Examples 9 to 12

Compositions were obtained in the same manner as that of the workingexamples 10 to 13 except that there was used 100 parts of adimethylpolysiloxane having the terminal ends of its molecular chainblocked by trimethoxysiloxy groups, instead of 100 parts of adimethylpolysiloxane having both terminal ends of its molecular chainblocked by trimethoxysilyl-ethylene groups.

Comparative Example 13

A composition was obtained by mixing together 100 parts of thedimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 0.5 parts of a dioctyl tindilaurate, in an environment where moisture was blocked, until a uniformconsistency was achieved.

Comparative Example 14

A composition was obtained by mixing together 100 parts of thedimethylpolysiloxane (polymer B) having both terminal ends of itsmolecular chain blocked by trimethoxysilyl-ethylene groups andexhibiting a viscosity of 970 mPa·s; and 1 part of adiazabicycloundecene, in an environment where moisture was blocked,until a uniform consistency was achieved.

Test

A tack-free time of each composition prepared in the working examples 10to 14 and the comparative examples 5 to 14, was measured.

Further, each freshly obtained composition of the working examples 10 to14 and the comparative examples 5 to 14 was pushed out into the shape ofa sheet having a thickness of 2 mm, followed by exposing the same to anair of 50% RH at 23° C. Next, the properties (initial properties) of acured product obtained by leaving such sheet under the same atmospherefor 7 days were measured in accordance with JIS K-6249. Here, thehardness of the cured product was measured using a durometer A incompliance with JIS K-6249.

In addition, similar measurements were performed on a product obtainedby storing the aforementioned cured product in a thermo-hygrostat of 85°C. and 85% RH for 100 hours. Moreover, similar measurements were alsoperformed on a sheet of a thickness of 2 mm which had been made from aproduct prepared by placing each freshly obtained composition of theworking examples 10 to 14 and the comparative examples 5 to 14 in asealed container and then leaving the same there at 70° C. for 7 days.The results thereof are shown in the following tables.

TABLE 2 Working Working Working Working Working example 10 example 11example 12 example 13 example 14 Initial Hardness (Durometer A) 19 23 2130 21 Elongation at break (%) 120 110 70 60 105 Tensile strength (MPa)0.32 0.35 0.22 0.32 0.35 Endurance test Hardness (Durometer A) 23 28 2829 25 85° C., Elongation at break (%) 135 85 80 60 105 85% RH Tensilestrength (MPa) 0.42 0.33 0.32 0.28 0.28 Preservation test Hardness(Durometer A) 16 28 22 30 20 70° C., 7 days Elongation at break (%) 15090 150 75 110 Tensile strength (MPa) 0.29 0.37 0.36 0.36 0.27Discoloration test ΔE 1.4 1.8 1.6 2.1 2.3

TABLE 3 Comparative Comparative Comparative Comparative example 5example 6 example 7 example 8 Initial Hardness (Durometer A) 3 12 2 17Elongation at break (%) 100 225 290 95 Tensile strength (MPa) 0.05 0.140.05 0.23 Endurance test Hardness (Durometer A) 9 6 21 9 85° C., 85% RHElongation at break (%) 245 130 100 195 Tensile strength (MPa) 0.15 0.110.24 0.12 Preservation test Hardness (Durometer A) 2 16 2 16 70° C., 7days Elongation at break (%) 225 140 330 120 Tensile strength (MPa) 0.050.22 0.07 0.23 Discoloration test Δ E 1.7 0.2 1.5 0.4

TABLE 4 Comparative Comparative Comparative Comparative example 9example 10 example 11 example 12 Initial Hardness (Durometer A) 1 2 1 7Elongation at break (%) 50 140 110 90 Tensile strength (MPa) 0.02 0.060.05 0.12 Endurance test Hardness (Durorneter A) 3 24 6 21 85° C., 85%RH Elongation at break (%) 260 170 130 120 Tensile strength (MPa) 0.060.58 0.06 0.30 Preservation test Hardness (Durometer A) 1 4 1 8 70° C.,7 days Elongation at break (%) 50 250 110 85 Tensile strength (MPa) 0.030.07 0.04 0.16 Discoloration test Δ E 1.3 0.4 2.0 2.0

TABLE 5 Comparative Comparative example 13 example 14 Initial Hardness(Durometer A) 26 26 Elongation at break (%) 90 75 Tensile strength (MPa)0.36 0.38 Endurance test Hardness (Durometer A) 27 27 85° C., 85% RHElongation at break (%) 95 80 Tensile strength (MPa) 0.38 0.37Preservation test Hardness (Durometer A) 13 27 70° C., 7 days Elongationat break (%) 90 70 Tensile strength (MPa) 0.16 0.35 Discoloration test ΔE 2.0 5.1

According to the results shown in the above tables, it is obvious thatthe fast curabilities observed in the working examples 10 to 14 wereextremely higher than those of the corresponding comparative examples 5to 14. Further, it is obvious that the working example 13 exhibited apreservation stability and durability that were significantly higherthan those of the comparative example 8.

However, the present invention is not limited to the aforementionedworking examples. The above working examples are simply shown asexamples, and anything having a framework substantially identical to thetechnical idea(s) as set forth in the claims of the present applicationand bringing about similar effects shall be included in the technicalscope of the present invention.

1.-9. (canceled)
 10. An aluminum chelate compound having a β-dicarbonylcompound represented by the following general formula (1):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms; and A is a grouprepresented by the following formula (2) or a group represented by —OR⁸:

wherein each of R⁵ to R⁷ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R⁵ to R⁷ being either identical to or different from one another; and R⁸represents a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 5 carbon atoms), provided that an average coordinationnumber of said β-dicarbonyl compound represented by the general formula(1) to aluminum is 0.5 to 2.5.
 11. The aluminum chelate compoundaccording to claim 10, having a β-ketoester represented by the followingformula (3) and a diketone represented by the following formula (4):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; and R⁸represents a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 5 carbon atoms)

(wherein each of R⁹ and R¹⁰ represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, R⁹ and R¹⁰being either identical to or different from each other; and R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms), provided that an averagemolecular coordination number of said β-ketoester represented by theformula (3) to aluminum is 0.5 to 2.5, an average molecular coordinationnumber of said diketone represented by the formula (4) to aluminum is0.5 to 2.5, and an average molecular coordination number of a total ofthe formulae (3) and (4) is 3.0.
 12. The aluminum chelate compoundaccording to claim 10, having a diketone represented by the followingformula (5) and a β-ketoester represented by the following formula (6):

(wherein each of R¹ to R³ represents a halogen atom or a substituted orunsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms,R¹ to R³ being either identical to or different from one another; R⁴represents a hydrogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms; and each of R⁵ to R⁷represents a halogen atom or a substituted or unsubstituted monovalenthydrocarbon group having 1 to 12 carbon atoms, R⁵ to R⁷ being eitheridentical to or different from one another)

(wherein R¹¹ represents a linear monovalent hydrocarbon group having 1to 12 carbon atoms; and R⁸ represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 5 carbon atoms), provided thatan average molecular coordination number of said diketone represented bythe formula (5) to aluminum is 0.5 to 2.5, an average molecularcoordination number of said β-ketoester represented by the formula (6)to aluminum is 0.5 to 2.5, and an average molecular coordination numberof a total of the formulae (5) and (6) is 3.0.
 13. A resin curingcatalyst comprising the aluminum chelate compound of claim
 10. 14. Aroom temperature-curable resin composition comprising: (A) 100 parts bymass of an alkoxysilyl-ethylene group terminated polymer having in onemolecule at least one structure represented by the following generalformula:

(wherein each of R¹ and R² represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, R¹ and R²being either identical to or different from each other; and a represents2 or 3); and (D) 0.001 to 15 parts by mass of an aluminum chelatecompound according to claim
 10. 15. A room temperature-curableorganopolysiloxane composition comprising: (B) 100 parts by mass of adiorganopolysiloxane having in one molecule at least two silicon atoms,each silicon atom being bonded to a hydroxyl group and/or a hydrolyzablegroup; (C) 0.1 to 30 parts by mass of an alkoxysilyl-ethylenegroup-containing compound having in one molecule at least one structurerepresented by the following general formula:

(wherein each of R¹ and R² represents a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, R¹ and R²being either identical to or different from each other; a represents 2or 3; and n represents an integer of 0 to 10); and (D) 0.001 to 15 partsby mass of an aluminum chelate compound according to claim
 10. 16. Amolded product obtained by curing the room temperature-curable resincomposition of claim
 14. 17. A molded product obtained by curing theroom temperature-curable resin composition of claim
 15. 18. A coating,adhesive or sealing agent comprising the room temperature-curable resincomposition of claim
 14. 19. A coating, adhesive or sealing agentcomprising the room temperature-curable resin composition of claim 15.